EP1956051A2 - Pigments de phtalocyanine à double ton métallique neutre - Google Patents

Pigments de phtalocyanine à double ton métallique neutre Download PDF

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Publication number
EP1956051A2
EP1956051A2 EP07015326A EP07015326A EP1956051A2 EP 1956051 A2 EP1956051 A2 EP 1956051A2 EP 07015326 A EP07015326 A EP 07015326A EP 07015326 A EP07015326 A EP 07015326A EP 1956051 A2 EP1956051 A2 EP 1956051A2
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Prior art keywords
pigment
water
group
dispersing resin
pigment composition
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EP07015326A
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German (de)
English (en)
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EP1956051A3 (fr
EP1956051B1 (fr
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Bethany J. Wolf
Wengan Wu
Brian Thompson
Richard K. Faubion
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Sun Chemical Corp
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Sun Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/0089—Non common dispersing agents non ionic dispersing agent, e.g. EO or PO addition products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0005—Coated particulate pigments or dyes the pigments being nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
    • C09B67/0016—Influencing the physical properties by treatment with a liquid, e.g. solvents of phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0022—Wet grinding of pigments
    • C09B67/0023—Wet grinding of pigments of phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes

Definitions

  • the present invention relates to phthalocyanine pigments, in particular, copper phthalocyanine pigments and compositions thereof that are prepared without requiring the use of sulfonated or anionic phthalocyanine complexes and yet exhibit an excellent metallic down travel.
  • the pigments and the compositions are compatible with waterborne coating systems and especially useful for automotive painting applications.
  • Chlorinated copper phthalocyanine pigments have been a considerable problem in this area as their attributes in waterborne systems have always been less desirable than their solventborne equivalents.
  • U.S. Patent No. 5,725,649 discloses chlorinated copper phthalocyanine containing 0-4 chlorine atoms having a crystal size in the range of from 0.01 to 0.2 ⁇ m and an ionic complex formed from copper phthalocyanine sulphonic acid and a quaternary amine. This product is produced by either acid pasting or salt ball milling followed by a solvent treatment and exhibits a green down flop in metallic paints.
  • 5,728,204 discloses a water-dispersible phthalocyanine pigment in combination with a sulfonated copper phthalocyanine, having a mean particle size of about 0.2 to about 0.3 ⁇ m and exhibiting a neutral metallic down flop.
  • the copper phthalocyanine pigment is processed by ball milling without salt followed by optional solvent treatment.
  • both of these prior patents require the use of copper phthalocyanine derivatives, such as sulfonated, anionic phthalocyanine complexes, to obtain the desired effect.
  • copper phthalocyanine derivatives have been implicated in paint film problems, such as poor humidity resistance and occurrences of delamination.
  • the present invention provides phthalocyanine pigments and compositions thereof that are suitable for waterborne coating systems, particularly useful for automotive painting applications.
  • the present invention provides phthalocyanine pigments having a narrow particle-size distribution, as reflected by a specific polydispersity value defined below, which achieve the desired substantially neutral down travel in metallic paint films.
  • the terms “travel”, “down travel” and “down flop” used interchangeably herein all refer to a change in apparent color value of a metallic paint film when measured from a 15° to 110° viewing angle.
  • phthalocyanine pigments of the present invention are metallophthalocyanine pigments and the metal of the metallophthalocyanine is most preferably copper.
  • the present invention provides copper phathalocyanine pigments that have excellent dispersibility in waterborne systems and exhibit an attractive substantially neutral down travel.
  • the copper phthalocyanine pigment of the present invention has a narrow particle size distribution with 90% of particles between about 0.01 ⁇ m and about 0.10 ⁇ m, an overall average particle size of no more than about 0.05 ⁇ m, a D99 of no more than about 0.3 ⁇ m, and a polydispersity of about 2.0 or less.
  • the term "D99” used herein refers to the size to which particles of 99 wt% of the tested samples is smaller than or equal.
  • polydispersity used herein refers to a ratio of the weight/volume average size (Dw) to the number average size (Dn), that is, Dw/Dn and indicates the distribution of individual particle size in a batch of pigment.
  • the copper phthalocyanine pigment of the present invention may or may not contain chlorine atoms. Typically, the copper phthalocyanine pigment containing 0-4 chlorine atoms is most preferable, but those containing more than 4 chlorine atoms may be also used.
  • the present invention further provides a pigment composition comprising the pigment of the present invention and a water-based polymeric dispersing resin.
  • the present invention provides a process for producing the pigment and the composition of the present invention.
  • ink compositions containing the pigments or pigment compositions of the invention as well as coatings, such as paint coatings, comprising the pigments or pigment compositions of the invention are also provided.
  • the present invention generally relates to water-dispersible phthalocyanine pigments, in particular, metallophthalocyanine pigments having a narrow particle-size distribution as reflected by a specific polydispersity value.
  • the metal of the metallophthalocyanine may be any metals that are commonly used to form metallophthalocyanine, including, but not limited to, copper, iron, zinc, cobalt, platinum, chromium, nickel, palladium, and so forth.
  • the most preferred phtahlocyanine pigments are chlorinated copper phtalocyanine pigments, but any other phthalocyanine pigments or metallophthalocyanine pigments, unsubstituted or substituted with, for example, halogens, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or other substituents typical of phthalocyanine pigments, are also encompassed by the present invention so long as the pigments have the same size-characteristics as described below.
  • the present invention is based on the discovery by the present inventors that a copper phthalocyanine pigment optionally containing chlorine atoms, having a particle-size distribution with 90% of particles between about 0.01 ⁇ m and about 0.10 ⁇ m, an overall average particle size of no more than about 0.05 ⁇ m, a D99 of no more than about 0.3 ⁇ m, and a polydispersity of about 2.0 or less, exhibits a better down travel than the currently available commercial products.
  • the pigments and the compositions containing the same are compatible with waterborne coating systems and useful in the automotive industry.
  • the pigments and the composition of the present invention can be also used for preparing ink compositions.
  • Crude copper phthalocyanine to be used for preparing the pigment of the present invention can be obtained by any method known to one skilled in the art.
  • chlorinated copper phthalocyanine blue crude can be obtained by a reaction of suitable amount of 4-chlorophthalic acid, phthalic anhydride or a derivative thereof, urea and a copper source, such as cuprous chloride, or by a reaction of 4-chlorophthalic acid, phthalonitrile or a derivative thereof and a copper source in an organic solvent, in the presence or absence of a catalyst, such as ammonium molybdate or titanium tetrachloride.
  • a catalyst such as ammonium molybdate or titanium tetrachloride.
  • previously prepared copper phthalocyanine may be chlorinated in a molten chlorine salt, such as aluminum chloride/titanium tetrachloride melt and preferably an aluminum chloride/sodium chloride melt, or in chlorosulfonic acid.
  • a molten chlorine salt such as aluminum chloride/titanium tetrachloride melt and preferably an aluminum chloride/sodium chloride melt, or in chlorosulfonic acid.
  • the crude pigment is first dry milled to a subpigmentary particle size.
  • the dry milling step can be carried out using procedures known in the art, such as ball milling.
  • dry milling is preferably carried out at temperatures below about 80°C and preferably at about 40° to 50°C. Milling must be carried out for a sufficient length of time to allow the particles to reach the desired size range (as determined, for example, by X-ray analysis), but the length of time is not otherwise critical. In general, a period of from about 6 hours up to about 24 hours is sufficient, with the preferred time generally depending on the capacity of the mill used. For example, milling with a laboratory mill might take 2 or 3 days, whereas milling with a plant-scale mill might take only 8 to 12 hours.
  • the milled pigment is then conditioned by mixing (for example, by stirring) with a conditioning solvent mixture comprising water and an aromatic carboxylic acid ester, optionally in the presence of a dispersant.
  • a conditioning solvent mixture comprising water and an aromatic carboxylic acid ester, optionally in the presence of a dispersant.
  • the water and ester can be combined with the milled pigment separately or premixed.
  • stirrable slurries typically contain at least about 2 parts by weight of water and about 0.2 part by weight of the ester for each part of the crude pigment. In general, about 3 to about 6 parts by weight, preferably 4 to 5 parts by weight, of water and about 0.4 to about 1.2 parts by weight, preferably 0.6 to 0.8 parts by weight, of the ester for each part of crude pigment, has been found particularly advantageous to use. Larger quantities of solvent, although effective, are unnecessary and may even be undesirable for economic and environmental reasons.
  • the esters in the conditioning solvent mixture are preferably C 1 -C 12 alkyl esters of C 6 -C 12 monocarboxylic and/or dicarboxylic acids.
  • Suitable aromatic monocarboxylic acids include, but not the way of limitation, benzoic acid and naphthoic acids and isomeric forms thereof, as well as aromatic ring-substituted derivatives in which the substituent can be, for example, alkyl, alkoxy, alkanoyl, halogen, hydroxy, amino, nitro, vinyl, and allyl groups.
  • Suitable aromatic dicarboxylic acids include phthalic, isophthalic, terephthalic, and naphthalic acids and the isomeric forms thereof, as well as aromatic ring-substituted derivatives.
  • Suitable C 1 -C 12 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomeric forms thereof.
  • Esters of dicarboxylic acids can contain two different alkyl groups, although esters having identical alkyl groups are preferred.
  • Preferred organic solvents include C 1 -C 4 alkyl esters of benzoic, phthalic, and salicylic acids, particularly methyl benzoate, methyl salicylate, and dimethyl phthalate. Mixtures of such esters are also suitable. Esters of aromatic tricarboxylic and tetracarboxylic acids can be used but are less preferred.
  • the conditioning solvent mixture may optionally contain a dispersant.
  • Suitable dispersants include homopolymers or copolymers of ethylenically unsaturated monomers, such as (meth)acrylic acids or corresponding alkyl or hydroxyalkyl esters, polyester, polyurethane, styrene-maleic anhydride copolymers (e.g., SMA ® Resins), various forms of rosin or polymerized rosin, alkali metal salts of sulfosuccinate esters, alkylene oxide polymers or copolymers, and so forth.
  • SMA ® Resins styrene-maleic anhydride copolymers
  • the conditioning step can be carried out at temperatures in the range of, for example, from about 30°C to about 145°C. In general, however, temperatures below about 70°C are less preferred because of a tendency to give less readily dispersed pigment. Furthermore, although temperatures above about 90°C can be used, they are less preferred because of potential overgrowth of crystals. Conditioning must be carried out for a sufficient length of time to allow the particles to attain optimum pigmentary size and distribution. Conditioning times typically range from at least about 4 hours, preferably at least 8 hours, to about 12 hours, but the length of time is not otherwise critical.
  • Isolation of the conditioned pigment can be carried out by any of several methods known in the art. Although it is possible in theory to remove the solvent by physical separation methods, it has been found advantageous to hydrolyze the esters of aromatic carboxylic acids and their by-products removed before the pigment is collected. Hydrolysis of such esters can be carried out, for example, by heating the solvent-containing conditioned pigment with a strongly alkaline solution, preferably an aqueous solution, such as aqueous sodium or potassium hydroxide. A particularly preferred hydrolysis method involves heating the solvent-containing pigment for about 2 hours at about 85°C in about 4 to about 10% aqueous sodium hydroxide prepared, for example, by adding 50% aqueous sodium hydroxide directly to the aqueous conditioning mixture. Other hydrolysis methods known in the art may be also suitable. The carboxylate and alcohol by-products formed during hydrolysis can then be removed (and recovered if desired), for example, during the separation step.
  • the pigment can be collected by methods known in the art, preferably filtration, and then dried. Other collection methods known in the art, such as centrifugation, may be also suitable, but are generally less preferred.
  • the hydrolysis by-products can be easily removed by washing the pigment filter cake, preferably, with water. The pigment is then dried for finishing.
  • the resulting dried pigment is ground within a high-shear mixer containing about 1 to about 10 parts by weight, preferably about 4 to 6 parts by weight, of an inorganic salt per part of organic pigment and about 1 to about 5 parts by weight, preferably about 1 to 2 parts by weight, of a liquid in which the organic pigment and salt are substantially insoluble.
  • Suitable salts for salt grinding include sodium chloride, potassium chloride, calcium chloride, zinc chloride, aluminum chloride, sodium sulfate, aluminum sulfate, calcium carbonate, sodium acetate, calcium acetate, sodium citrate, potassium sodium tartrate, and so forth.
  • Sodium chloride is particularly convenient and preferred.
  • Suitable liquids for use in salt grinding are liquids, preferably organic liquids or low-melting solids that liquefy during grinding, in which the organic pigment and salt are substantially insoluble but which enable the physical transformation of crude pigments into finished pigments to occur when carrying out the process of the present invention.
  • suitable organic liquids include alcohols, such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or glycerin; lower organic acids, such as formic or acetic acid; ethers such as dioxane, tetrahydrofuran, ethylene glycol monoethyl or diethyl ether, or oligo- and polyglycol ethers; ketones, such as acetone or methyl ethyl ketone; aromatics, such as toluene, xylene, chlorobenzene, nitrobenzene, or chloronaphthalene; esters, such as methyl benzoate, dimethyl phthalate, or methyl salicylate; and amides, such as formamide, dimethylformamide, or N-methylpyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or
  • Preferred organic liquids are glycols, particularly ethylene glycol and propylene glycol. It is possible, though generally less preferred, to include small amounts of water that should not exceed 50% of the total amount of liquid, including the amount of water that may be present in the crude pigment. Although virtually any high-shear mixer can be used, continuous sigma blade high-shear mixers are preferred.
  • the initial grinding step (a) is carried out at a temperature of about 0°C to about 100°C, preferably 30°C to 60°C, for a period sufficient to produce a uniform paste; for example, for at least one hour but no more than 24 hours, preferably for about two to ten hours, and most preferably for about 5 hours.
  • a relatively large amount of the liquid which will usually produce a thin pigment mass
  • the pigment mass becomes too thick during the grinding step, either due to the evaporation of the liquid or the formation of finer pigment particles, it may be desirable to add small amounts of the liquid to maintain effective and efficient grinding.
  • step (b) the pigment paste from step (a) is mixed with water, which may optionally contain or be treated with an acid and/or various organic liquids, which are preferably water-miscible organic liquids.
  • Acids that are capable of forming soluble metal salts can be added during step (b) to help remove metal or metal oxide contaminants from the pigment mass.
  • Suitable acids include mineral acids, such as hydrochloric acid and sulfuric acid, and at least moderately acidic organic acids, such as acetic acid, trifluoroacetic acid, and citric acid.
  • Suitable organic liquids for use in step (b) include, but not limited to, lower aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or glycerin; ketones and ketoalcohols, such as acetone, methyl ethyl ketone, and diacetone alcohol; amides, such as dimethylformamide and dimethylacetamide; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and triols, such as ethylene glycol and glycerol; and so forth that are known in the art.
  • lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or glycerin
  • ketones and ketoalcohols such as acetone, methyl ethyl ketone, and diacetone alcohol
  • amides
  • organic liquids may be used but are generally much less preferred. If a low volatile water-immiscible organic liquid is used at any step in the process of the invention, it may be necessary to wash the pigment in two steps: first, with water to remove salts and other watersoluble materials and second, with a more volatile organic solvent to remove the remaining organic materials.
  • the water or organic liquids in step (b) may optionally contain a dispersant, for example, those described above.
  • Step (b) is carried out by stirring the pigment mixture, for a period sufficient to dissolve the inorganic salt, essentially at any temperature at which the mixture does not freeze or boil; for example, at a temperature range of about 0°C to about 100°C for aqueous mixtures. However, temperatures near the boiling point of the mixture, i.e., typically about 90°C to about 95°C are generally preferred. When the mixture contains an organic solvent, the temperature varies depending on the solvent.
  • the finished pigment thus obtained is collected in step (c) by methods known in the art, preferably by filtration followed by washing to remove residual acid. Other collection methods known in the art, such as membrane filtration, centrifugation, or even simple decantation, are also suitable but generally less preferred.
  • the resulting pigment may be dried for use, but is most preferably reslurried for further conditioning. Drying may be carried out using conventional drying methods, such as spray drying, tray drying, drum drying, and so forth; however, spray drying is most preferable.
  • the pigment may be reslurried in water, water-miscible solvent, or mixture thereof, for further conditioning prior to spray drying. If reslurried in water only, the slurry can be spray-dried directly or heated to temperatures between about 25°C and about 95°C, preferably between about 25°C and about 70°C, before spray-drying. If reslurried in water-miscible solvent or mixture of water and water-miscible solvent, the slurry is conditioned at a temperature of about 25°C to about 150°C, preferably about 90°C to about 120°C. If the conditioning is above the boiling point of the solvent mixture, this step is carried out under pressure.
  • a conditioning time of from about 30 minutes to about ten hours is sufficient, with preferred times being about 2-6 hours.
  • Suitable water-miscible solvents may include alcohols, such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or glycerin; or ketones, such as acetone, methyl ethyl ketone, diacetone alcohol, methyl isopropyl ketone, methyl amyl ketone, methyl n-butyl ketone, or N-methyl-pyrrolidone, and so forth.
  • alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, or glycerin
  • ketones such as acetone, methyl ethyl ketone, diacetone alcohol, methyl isopropyl ketone, methyl amyl ketone, methyl n-butyl ketone
  • the pigment slurry should contain about 5% to 75%, preferably about 15% to 50%, and most preferably about 25% to 35 % of active resin dispersant based on the pigment weight.
  • Suitable resin dispersants include, but not limited to, ethylenically unsaturated monomers, homopolymers or copolymers of (meth)acrylic acids or corresponding alkyl or hydroxyalkyl esters, polyester, polyurethane, styrene-maleic anhydride copolymers (e.g., SMA ® Resins, by Sartomer Company Inc., PA), various forms of rosin or polymerized rosin, alkali metal salts of sulfosuccinate esters, alkylene oxide polymers or copolymers, and so forth.
  • SOLSPERSE ® 27000 Noveon Inc., OH
  • DISPERBYK ® -190 BYK Chemie, Germany
  • Borchi ® Gen SN 95 Borchers GmbH, Germany
  • SOLSPERSE ® 27000, CAS NO. 35545-57-4 a polymer of the formula: wherein n is a number such that the average molecular weight is in the range of about 1000-1100.
  • the pigments produced in the examples below were evaluated for their Travel dH in an automotive waterborne basecoat/solventborne clearcoat system as follows:
  • the pigments were dispersed into the waterborne basecoat at a pigment loading of 16.4% after pH adjustment to 8.0 ⁇ 0.15 using a Skandex paint conditioner for 6 hours.
  • This dispersion stage included a solublized acrylic resin, propylene glycol monomethyl ether, and a polypropylene glycol resin.
  • the mixture is then reduced to 14% with distilled water and an acrylic latex solution.
  • the dispersion is incorporated into waterborne paints with a ratio of 1:1 color:TiO 2 and 1:1 color:Aluminum.
  • the paints are sprayed onto a coilcoat-primed aluminum panel at a film thickness of 25 ⁇ 5 microns, baked at 200°F, and then a solventborne acrylic clearcoat is sprayed over the basecoat at a film thickness of 50 ⁇ 5 microns and baked at 260°F.
  • the sprayed aluminum paint panels are evaluated on an X-Rite MA-58 multi-angle spectrophotometer to give a 5-angle representation of the color performance versus the standard.
  • chlorinated copper phthalocyanine pigment 428-4816 (Sun Chemical Corporation, OH), was used.
  • the particle sizes of each pigment preparation were determined by a disk centrifuge particle size (DCP) analyzer (Brookhaven Instrument Corporation, NY).
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake.
  • Fifty (50) grams dry weight of the presscake were then slurried in water at 20.0% total solids with a high shear mixer.
  • the slurry was spray dried. The down travel, particle size, and polydispersity are shown in Table 1.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment is then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake.
  • Fifty (50) grams dry weight of the presscake were then slurried in water with 25.0% active Solsperse ® 27000 resin based on pigment weight at 19% total solids with a high shear mixer.
  • the slurry was spray dried. The down travel, particle size, and polydispersity are shown in Table 1.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake.
  • Fifty (50) grams dry weight of the presscake were then slurried in methanol at 15% solids with a high shear mixer and conditioned at 120°C for three hours.
  • the slurry was cooled to 60°C and drowned into 300 g water.
  • the methanol was distilled off and the resultant slurry was spray dried.
  • the down travel, particle size, and polydispersity are shown
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake and dried. Thirty-two (32) grams of product were charged to a sigma blade mixer/kneader along with 243 g of salt and 60 g of propylene glycol and ground for five hours.
  • the paste was discharged from the mixer/kneader into 800 g of water.
  • the pH is adjusted to 2.0-2.5 with concentrated HCl, heated to 90°C for one hour and isolated.
  • the presscake was reslurried in 600 g of water and spray dried. The down travel, particle size, and polydispersity are described in Table 1.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • the 50 grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids. Subsequently, the slurry was conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the thus-prepared product was isolated as presscake and dried. Thirty-two (32) grams of the product were charged to an attritor along with 243 g of salt and 60 g of propylene glycol and ground for five hours.
  • the resulting paste was discharged from the attritor into 800 g of water and the pH was adjusted to 2.0-2.5 with concentrated HCl.
  • the presscake was isolated after being heated to 90°C for one hour in the water.
  • the presscake was reslurried in 300 g of water with 30.0% active SOLSPERSE 27000 resin, based on the weight of the pigment, and spray dried.
  • the down travel, particle size, and polydispersity of the resultant pigment composition are shown in Table 1.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • Fifty (50) grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake and dried. Thirty-two (32) grams of product were charged to an attritor along with 243g of salt and 60g of propylene glycol and ground for five hours.
  • the paste was discharged from the attritor into 800g of water.
  • the pH was adjusted to 2.0-2.5 with concentrated HCl, and the presscake was heated to 90°C for one hour and isolated.
  • the presscake was reslurried in 200 g of methanol and conditioned at 120°C for three hours. Three- hundred (300) ml of water were added and the methanol was distilled off prior to spray-drying.
  • the down travel, particle size, and polydispersity are shown in Table 1.
  • Chlorinated copper phthalocyanine blue crude was charged to a ball mill to realize a ratio of 1 to 10 parts pigment to balls.
  • the crude pigment was then milled for 12-24 hours at no more than 70°C.
  • the 50 grams of the resulting crude were then slurried in 15% methyl benzoate/water at 15-17% solids.
  • the slurry was then conditioned at 85°C for 8 hours.
  • the methyl benzoate was hydrolyzed with excess sodium hydroxide to remove the methyl benzoate.
  • the product was isolated as presscake and dried. Thirty-two (32) grams of the product was charged to a sigma blade mixer/kneader along with 243 g of salt and 60 g of propylene glycol and ground for five hours.
  • the paste was discharged from the mixer/kneader into 800 g of water and the pH was adjusted to 2.0-2.5 with concentrated HCl.
  • the presscake was isolated after being heated to 90°C for one hour.
  • the presscake was reslurried in 200 g of methanol with 30.0% active SOLSPERSE 27000 resin, based on the weight of the pigment, and conditioned at 120°C for three hours. Two-hundred (200) ml of water were added and the methanol was distilled off prior to spray drying.
  • the down travel, particle size, and polydispersity of the resulting pigment composition are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP07015326A 2006-08-09 2007-08-04 Pigments de phtalocyanine à double ton métallique neutre Active EP1956051B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/463,545 US7323046B1 (en) 2006-08-09 2006-08-09 Phthalocyanine pigments with neutral metallic down flop

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EP1956051A2 true EP1956051A2 (fr) 2008-08-13
EP1956051A3 EP1956051A3 (fr) 2010-04-28
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016196715A1 (fr) * 2015-06-04 2016-12-08 Sun Chemical Corporation Pigments de phthalocyanine de cuivre chlorés
WO2018085346A1 (fr) * 2016-11-03 2018-05-11 Sun Chemical Corporation Compositions de pigments contenant des pigments chlorés de phtalocyanine de cuivre sous la forme de cristaux gamma
CN110016273A (zh) * 2019-04-28 2019-07-16 刘子瑄 一种用于塑胶金属类材质上的水性涂料及其制备方法

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WO2008022280A2 (fr) * 2006-08-18 2008-02-21 Sun Chemical Corporation Pigments à haute transparence
US7763107B2 (en) * 2007-12-27 2010-07-27 Brother Kogyo Kabushiki Kaisha Ink for ink-jet recording and ink set for ink-jet recording
CN102363675B (zh) * 2011-10-08 2014-05-21 吉洵 一种酞菁蓝及其制造工艺
GB201721808D0 (en) * 2017-12-22 2018-02-07 Sensient Colors Uk Ltd Nanaoparticle dispersions

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US5728204A (en) 1996-01-31 1998-03-17 Bayer Corporation Preparation of phthalocyanine-containing waterborne coating systems
EP1116757A2 (fr) 2000-01-11 2001-07-18 Ricoh Company, Ltd. Dispersion pigmentaire et composition d'encre pour impression par jet l'utilisant
JP2004149632A (ja) 2002-10-29 2004-05-27 Ricoh Co Ltd 顔料分散液及びそれを用いたインクジェット用インクの製造方法

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JPH0826253B2 (ja) * 1990-12-21 1996-03-13 大日精化工業株式会社 メタリック塗料組成物
ES2095002T3 (es) * 1992-02-11 1997-02-01 Zeneca Ltd Dispersion.
US5284511A (en) * 1993-04-12 1994-02-08 Miles Inc. Conditioning process for phthalocyanine pigments
JP3533678B2 (ja) * 1993-09-01 2004-05-31 大日本インキ化学工業株式会社 印刷インキ又は印刷インキ用顔料ペーストの製造方法
GB9517565D0 (en) * 1995-08-26 1995-10-25 Ciba Geigy Ag Pigment compositions
JP3371685B2 (ja) * 1996-04-30 2003-01-27 ぺんてる株式会社 水性顔料インキ
US6063182A (en) * 1997-09-08 2000-05-16 Ciba Speciality Chemicals Corporation Stir-in pigment compositions
JP3706477B2 (ja) * 1998-03-02 2005-10-12 東洋インキ製造株式会社 インクジェットインキの製造方法
US7563835B2 (en) * 2001-12-28 2009-07-21 Sun Chemical Corporation Solventless universal colorants
US6726755B2 (en) * 2002-02-08 2004-04-27 Xerox Corporation Ink compositions containing phthalocyanines
JP2004149633A (ja) * 2002-10-29 2004-05-27 Ricoh Co Ltd 顔料系インクジェット用インク及び該インクの製造方法
DE10253804A1 (de) * 2002-11-18 2004-05-27 Basf Ag Feste Pigmentzubereitungen, enthaltend wasserlösliche anionische carboxylatgruppenhaltige oberflächenaktive Additive

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US5728204A (en) 1996-01-31 1998-03-17 Bayer Corporation Preparation of phthalocyanine-containing waterborne coating systems
EP1116757A2 (fr) 2000-01-11 2001-07-18 Ricoh Company, Ltd. Dispersion pigmentaire et composition d'encre pour impression par jet l'utilisant
JP2004149632A (ja) 2002-10-29 2004-05-27 Ricoh Co Ltd 顔料分散液及びそれを用いたインクジェット用インクの製造方法

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Publication number Priority date Publication date Assignee Title
CN107922750B (zh) * 2015-06-04 2020-07-10 太阳化学公司 氯化铜酞菁颜料
US10544307B2 (en) 2015-06-04 2020-01-28 Sun Chemical Corporation Chlorinated copper phthalocyanine pigments
CN107922750A (zh) * 2015-06-04 2018-04-17 太阳化学公司 氯化铜酞菁颜料
CN111777870B (zh) * 2015-06-04 2022-06-07 太阳化学公司 氯化铜酞菁颜料
KR102360691B1 (ko) 2015-06-04 2022-02-08 썬 케미칼 코포레이션 염화된 구리 프탈로시아닌 안료
KR102007600B1 (ko) 2015-06-04 2019-08-05 썬 케미칼 코포레이션 염화된 구리 프탈로시아닌 안료
KR20180012305A (ko) * 2015-06-04 2018-02-05 썬 케미칼 코포레이션 염화된 구리 프탈로시아닌 안료
KR20190091570A (ko) * 2015-06-04 2019-08-06 썬 케미칼 코포레이션 염화된 구리 프탈로시아닌 안료
CN111777870A (zh) * 2015-06-04 2020-10-16 太阳化学公司 氯化铜酞菁颜料
WO2016196715A1 (fr) * 2015-06-04 2016-12-08 Sun Chemical Corporation Pigments de phthalocyanine de cuivre chlorés
CN110099967A (zh) * 2016-11-03 2019-08-06 太阳化学公司 含有γ晶型氯化铜酞菁颜料的颜料组合物
US10711137B2 (en) 2016-11-03 2020-07-14 Sun Chemical Corporation Pigment compositions containing chlorinated copper phthalocyanine pigments in the gamma crystal form
WO2018085346A1 (fr) * 2016-11-03 2018-05-11 Sun Chemical Corporation Compositions de pigments contenant des pigments chlorés de phtalocyanine de cuivre sous la forme de cristaux gamma
CN110016273A (zh) * 2019-04-28 2019-07-16 刘子瑄 一种用于塑胶金属类材质上的水性涂料及其制备方法

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US7323046B1 (en) 2008-01-29
US20080035026A1 (en) 2008-02-14
EP1956051A3 (fr) 2010-04-28
EP1956051B1 (fr) 2012-10-31

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